US5248525A - Treating an autodeposited coating with an alkaline solution containing anions of multifunctional organic acids - Google Patents

Treating an autodeposited coating with an alkaline solution containing anions of multifunctional organic acids Download PDF

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US5248525A
US5248525A US07/718,676 US71867691A US5248525A US 5248525 A US5248525 A US 5248525A US 71867691 A US71867691 A US 71867691A US 5248525 A US5248525 A US 5248525A
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process according
acrps
acid
coating
anions
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Elizabeth J. Siebert
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Henkel Corp
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Henkel Corp
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Priority claimed from US07/645,435 external-priority patent/US5164234A/en
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Assigned to HENKEL CORPORATION A CORP. OF DE reassignment HENKEL CORPORATION A CORP. OF DE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: SIEBERT, ELIZABETH
Priority to US07/718,676 priority Critical patent/US5248525A/en
Priority to PCT/US1992/000490 priority patent/WO1992012806A1/fr
Priority to AU12658/92A priority patent/AU655632B2/en
Priority to CA002098830A priority patent/CA2098830C/fr
Priority to ES92904730T priority patent/ES2079855T3/es
Priority to DE69204053T priority patent/DE69204053T2/de
Priority to EP92904730A priority patent/EP0568619B1/fr
Priority to BR9205529A priority patent/BR9205529A/pt
Priority to JP4009858A priority patent/JP3012388B2/ja
Priority to MX9200318A priority patent/MX9200318A/es
Publication of US5248525A publication Critical patent/US5248525A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/142—Auto-deposited coatings, i.e. autophoretic coatings
    • B05D7/144—After-treatment of auto-deposited coatings

Definitions

  • Autodeposition involves the use of an aqueous resinous coating composition of relatively low solids concentration (usually less than about 10%) to form a coating of relatively high solids concentration (usually greater than about 10%) on a metallic surface immersed therein, with the coating increasing in thickness and areal density (mass per unit area of coating) the longer the time the metallic surface is immersed in the composition.
  • Autodeposition is somewhat similar to electrodeposition but does not require the aid of external electrical current to cause the resin particles to deposit on the metal surface.
  • autodepositing compositions are aqueous acid solutions having solid resin particles dispersed therein in very finely divided form.
  • the coating formed while the metal substrate used is immersed in the bath is generally wet and fairly weak, although sufficiently strong to maintain itself against gravity and moderate spraying forces. In this state the coating is described as "uncured”.
  • the uncured coated is dried, usually with the aid of heat. The coating is then described as "cured”.
  • the present invention relates more particularly to the chemical treatment of an uncured autodeposited coating for the purpose of improving various properties thereof, particularly the adhesion of the coating to the underlying metal substrate and the resistance to corrosion of the underlying metal provided by the cured autodeposited coating when the coated metal surfaced object is subjected to corrosive environments.
  • Basic constituents of an autodepositing composition are water, resin solids dispersed in the aqueous medium of the composition, and activator, that is, an ingredient or ingredients which convert the composition into one which will form on a metallic surface a resinous coating which increases in thickness or areal density as long as the surface is immersed in the composition.
  • activators or activating systems are known, for example, as reported in the following U. S. Pat. Nos.: 3,592,699; 3,709,743; 4,103,049; 4,347,172; and 4,373,050, the disclosures of Which, to the extent not inconsistent with any explicit statement herein, are hereby incorporated herein by reference.
  • the activating system generally comprises an acidic oxidizing system, for example: hydrogen peroxide and HF; HNO 3 ; a ferric-containing compound and HF; and other soluble metal-containing compounds, for example, silver fluoride, ferrous oxide, cupric sulfate, cobaltous nitrate, silver acetate, ferrous phosphate, chromium fluoride, cadmium fluoride, stannous fluoride, lead dioxide, and silver nitrate in an amount between about 0.025 and about 50 grams per liter (“g/l”) and an acid, which can be used alone or in combination with hydrofluoric acid, and including, for example, sulfuric, hydrochloric, nitric, and phosphoric acid, and organic acids, including, for example, acetic, chloroacetic, and trichloroacetic acids.
  • an acidic oxidizing system for example: hydrogen peroxide and HF; HNO 3 ; a ferric-containing compound and HF; and other soluble
  • Previously known autodepositing compositions can be used to form coatings which have good aesthetic properties and which protect the underlying metallic substrate from being degraded (for example, corroded by water).
  • Various means have been developed to improve the properties of autodeposited coatings, including, for example: chemical pretreatment of the metallic surface prior to formation of the coating; selection of particular resins for use in forming the coating; addition to the autodepositing composition of chemical additives; and chemical treatment of the freshly formed or uncured coating, as described in detail in copending application Serial No. 202,117 filed Jun. 3, 1988 and assigned to the same assignee as this application.
  • the '546 and '945 patents disclose treating an uncured autodeposited coating with an acidic aqueous solution containing hexavalent chromium or hexavalent chromium and formaldehyde-reduced forms of hexavalent chromium to improve the corrosion-resistant properties of the cured form of the coating and to reduce the gloss of an otherwise glossy coating.
  • the source of chromium can be chromium trioxide or water-soluble salts of chromium or dichromate, for example, sodium, potassium, and lithium salts thereof.
  • Optional ingredients of such chromium-containing solutions include phosphoric acid (anti-gelling agent), sodium hydroxide (pH adjuster), and a water-soluble or water-dispersible polyacrylic acid corrosion-resistant and paint-bonder improver).
  • phosphoric acid anti-gelling agent
  • sodium hydroxide pH adjuster
  • a water-soluble or water-dispersible polyacrylic acid corrosion-resistant and paint-bonder improver phosphoric acid (anti-gelling agent), sodium hydroxide (pH adjuster), and a water-soluble or water-dispersible polyacrylic acid corrosion-resistant and paint-bonder improver.
  • the '950 patent discloses the treatment of an uncured autodeposited coating with an aqueous chromium-containing solution which has dispersed therein particles of a resin which functions to impart to the cured form of the coating a reduced coefficient of friction.
  • the function of the chromium is to improve the corrosion-resistant properties of the cured coating, and the function of the resin, for example, polyt
  • the '839 patent discloses the treatment of an uncured autodeposited coating with an acidic aqueous treating solution prepared by admixing a hexavalent chromium-containing compound (for example, ammonium and an alkali metal dichromate) with a hexavalent chromium/reduced chromium solution.
  • the treating solution contains an acid or salt thereof, for example, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and ammonium, alkali metal, and alkaline earth metal salts of phosphoric acid.
  • This patent discloses that the use of such a solution imparts a matte appearance to an autodeposited coating which otherwise would have a glossy appearance and improves the corrosion-resistant properties of the coating.
  • U.S. Pat. No. 3,647,567 discloses the use of an acidic aqueous solution of chromium trioxide or of water-soluble or acid-soluble chromates and dichromates to improve the corrosion resistance of the resinous coatings described therein.
  • Exemplary chromates and dichromates are sodium, ammonium, lithium, magnesium, potassium and zinc.
  • Japanese Patent No. 7630247 discloses the treatment of an uncured autodeposited coating with an aqueous solution or dispersion of a vulcanizing agent (for example, a sulfur-containing compound) or of a vulcanizing accelerator (for example, hexamethylenetetramine) to improve the solvent resistance of the cured coating.
  • a vulcanizing agent for example, a sulfur-containing compound
  • a vulcanizing accelerator for example, hexamethylenetetramine
  • Japanese Patent No. 7630245 discloses the treatment of an uncured autodeposited coating with an aqueous composition containing a water-miscible coalescing agent comprising a compound having two or more oxygen-containing functional groups such as ester groups, hydroxy groups, carbonyl groups and ether linkages.
  • a water-miscible coalescing agent comprising a compound having two or more oxygen-containing functional groups such as ester groups, hydroxy groups, carbonyl groups and ether linkages.
  • oxygen-containing functional groups such as ester groups, hydroxy groups, carbonyl groups and ether linkages.
  • Examples of such classes of compounds include alcohols, ketones, alcohol esters, ketone esters, ketone ethers, and ester ethers.
  • This Japanese patent discloses that the treatment of uncured autodeposited coatings with such coalescing agents inhibits or deters the tendency of the cured form of the coating to blister, crack and/or bridge.
  • improvements in properties of cured autodeposited coatings are achieved by contacting the uncured form of the coatings with an alkaline aqueous solution that also contains a component selected from the group consisting of anions of multifunctional organic acids, in an amount sufficient to improve the corrosion resistance, adherence, or both corrosion resistance and adherence of the autodeposited coating after curing it.
  • Organic acids are considered to be multifunctional for the purposes of this invention when their molecules each contain at least two electron rich functional groups such as carboxyl and carbonyl, hydroxyl, ether, simple and substituted (but not quaternized) amino and amido, and phosphonyl.
  • molecules that contain different types of such functional groups are as useful as those that contain two or more of the same functional group type.
  • suitable acids include citric, oxalic, tartaric, and diphosphonic acids.
  • An advantage of the present invention is that improvements in the properties of autodeposited coatings can be realized by the use of a treating solution which does not require the presence of hexavalent chromium or a similarly toxic material which creates waste disposal problems.
  • One highly preferred type of acid from which anions needed in the treatment solutions according to this invention may be derived is the diphosphonic acids.
  • the general formula of a phosphonic acid is: ##STR1## where R 1 is a monovalent covalently bonded moiety containing at least one carbon atom and optionally also containing other functional groups, and R 2 is either a hydrogen atom or a monovalent covalently bonded moiety containing at least one carbon atom and optionally also containing other functional groups, and may be the same as R 1 or different.
  • Anions for use in this invention are preferably derived from phosphonic acids in which R 2 in the formula above is hydrogen.
  • the anions used in this invention are derived from acids having at least two (H 2 O 3 P) groups attached to a single carbon atom, e.g., from 1,1-diphosphonic acids having the general formula (H 2 O 3 P) 2 -CR 3 R 4 , wherein each of R 3 and R 4 may be independently selected from hydrogen, hydroxyl, monovalent alkyl, monovalent substituted alkyl, and (H 2 O 3 P) groups.
  • the most preferable anions are those of 1-hydroxyethylidene-1,1-diphosphonic acid, having the formula C(OH)(CH 3 )(PO 3 H 2 ) 2 .
  • organic anions for use in the treating solutions according to this invention are anions derived from citric, tartaric, and oxalic acids.
  • the pH of the solution used for treating an uncured autodeposited coating according to this invention is between 7 and 11, preferably between 7.5 and 10, more preferably between 8.2 and 9.0.
  • the concentration of the anions, expressed as their stoichiometric equivalent of the corresponding organic acid, is preferably between 0.05 and 5 percent by weight ("w/o"), more preferably between 0.2 and 2 w/o, most preferably between 0.5 and 1.5 w/o.
  • the acid may be neutralized with a base, preferably a fugitive base, i.e., a base which volatilizes at or below the temperature used in curing of the autodeposited coating that is treated according to this invention, and additional base may be added to achieve an alkaline pH.
  • a base preferably a fugitive base, i.e., a base which volatilizes at or below the temperature used in curing of the autodeposited coating that is treated according to this invention, and additional base may be added to achieve an alkaline pH.
  • the most preferred base for use in preparing a treating solution according to this invention is ammonium hydroxide.
  • Uncured film thickness treated are preferably from 12 to 50 micrometers (" ⁇ "), more preferably from 18 to 31 ⁇ .
  • Preferred coatings which are treated according to the process of the present invention are formed from an autodepositing composition in which particles of resin are dispersed in an aqueous acidic solution which is prepared by combining hydrofluoric acid and a soluble ferric iron-containing ingredient, most preferable ferric fluoride.
  • U.S. Pat. Nos. 4,347,172 and 4,411,937 which disclose the activating system preferred for use to form the autodeposited coatings to be treated according to this invention, disclose the optional use in the composition of an oxidizing agent in an amount to provide from about 0.01 to about 0.2 oxidizing equivalent per liter of composition.
  • Suitable oxidizing agents are those commonly known as depolarizers. Examples of oxidizing agents are hydrogen peroxide, dichromate, permanganate, nitrate, persulfate, perborate, p-benzoquinone and p-nitrophenol. Hydrogen peroxide is preferred.
  • Preferred resins for use in forming autodeposited coatings which are treated according to the present invention comprise internally stabilized vinylidene chloride copolymers or externally stabilized vinylidene chloride copolymers containing in excess of 50 w/o, or more preferably at least 80 w/o, of vinylidene chloride.
  • the vinylidene chloride copolymer is crystalline in nature.
  • Exemplary crystalline resins are described in U.S. Pat. No. 3,922,451 and aforementioned U.S. Pat. No. 3,617,368.
  • crystalline vinylidene chloride-containing resins comprise a relatively high proportion of vinylidene chloride, for example, at least about 80 wt. % thereof.
  • any resin suitable for use in an autodepositing composition can be used to form a coating to be treated according to this invention.
  • Internally stabilized polymers or resins include as part of their chemical structure a surfactant group which functions to maintain polymer particles or resin solids in a dispersed state in an aqueous medium, this being the function also performed by an "external surfactant", that is, by a material which has surface-active properties and which is absorbed on the surface of resin solids, such as those in colloidal dispersion.
  • an external surfactant that is, by a material which has surface-active properties and which is absorbed on the surface of resin solids, such as those in colloidal dispersion.
  • the presence of an external surfactant tends to increase the water sensitivity of coatings formed from aqueous resin dispersions containing the same and to adversely affect desired properties of the coatings.
  • the presence of undue amounts of surfactant in autodepositing compositions can lead to problems, as described in U.S. Pat. No.
  • surfactant is intended to be synonymous with the aforementioned.
  • Various types of internally stabilized vinylidene chloride-containing polymers are known and species thereof are available commercially. Examples of such latexes are the Saran latexes such as, for example, SARANTM 143 and SARANTM 112 available from W. R. Grace Co. and the SERFENETM latexes available from Morton Chemical. In accordance with the present invention, these commercial latexes can be used to excellent advantage, and internally stabilized latexes in general are preferred.
  • Various surfactants which function to maintain polymeric particles in dispersed state in aqueous medium include organic compounds which contain ionizable groups in which the anionic group is bound to the principal organic moiety of the compound, with the cationic group being a constituent such as, for example, hydrogen, an alkali metal, and ammonium.
  • exemplary anionic groups of widely used surfactants contain sulfur or phosphorous, for example, in the form of sulfates, thiosulfates, sulfonates, sulfinates, sulfaminates, phosphates, pyrophosphates and phosphonates.
  • Such surfactants comprise inorganic ionizable groups linked to an organic moiety.
  • the most widely used method for preparing such resins will involve reacting vinylidene chloride with a monomeric surfactant and optionally one or more other monomers.
  • the monomeric surfactant comprises a material which is polymerizable with monomeric vinylidene chloride or with a monomeric material which is polymerizable with monomeric vinylidene chloride and which is ionizable in the reaction mixture and in the acidic aqueous medium comprising an autodepositing composition.
  • a preferred class can be prepared by copolymerizing (A) vinylidene chloride monomer with (B) monomers such as methacrylic acid, methyl methacrylate, acrylonitrile, and vinyl chloride and (C) a water soluble ionic material such as sodium sulfoethyl methacrylate.
  • radical "R” is selected from the group consisting of vinyl and substituted vinyl, for example, alkyl-substituted vinyl; the symbol “Z” represents a difunctional linking group which will activate the double bond in the vinyl group; --Q-- is a divalent hydrocarbon moiety having its valence bonds on different carbon atoms; and the symbol "M + " represents a cation.
  • the relatively hydrophilic monomers of (2) above include those materials which are readily copolymerizable with (1) in aqueous dispersion, that is, which copolymerize within a period of about 40 hours at a temperature ranging from the freezing point of the monomeric serum up to about 100° C., and which have a solubility in both the water and the oil phase of the polymer latex of at least 1 weight percent at the temperature of polymerization.
  • Exemplary of preferred materials, particularly when used in conjunction with monomeric vinylidene chloride are methacrylic acid and methyl methacrylate.
  • hydroxyethyl and propyl acrylates include the hydroxyethyl and propyl acrylates, hydroxyethylmethacrylate, ethyl hexylacrylate, acrylic acid, acrylonitrile, methacrylonitrile, acrylamide, and the lower alkyl and dialkylacrylamides, acrolein, methyl vinyl ketone, and vinyl acetate.
  • copolymerizable ionic monomers used in preparing the aforementioned type resins are those monomeric materials which contain in their structure both an ionizable group and a reactive double bond, are significantly soluble in water, are copolymerizable with the hydrophilic monomer constituent (2) and in which the substituent on the double bond is chemically stable under the conditions normally encountered in emulsion polymerization.
  • Examples of the aforementioned divalent hydrocarbon moiety having its valence bonds on different carbon atoms include alkylene and arylene divalent hydrocarbon radical.
  • alkylene (CH 2 ) group can contain up to about 20 carbon atoms, it preferably has 2 to about 8 carbon atoms.
  • the solubility of the defined copolymerizable ionic material as described herein is strongly influenced by the cation M + .
  • Exemplary cations are the free acids, alkali metal salts, ammonium and amine salts and sulfonium and quaternary ammonium salts.
  • Preferred are the free acids, alkali metal salts, particularly sodium and potassium, and ammonium salts.
  • the solubility of the monomer depends on Q.
  • this group can be either aliphatic or aromatic and its size will determine the hydrophilic/ hydrophobic balance in the molecule, that is, if Q is relatively small, the monomer is water soluble, but as Q becomes progressively larger, the surface activity of such monomer increases until it becomes a soap and ultimately a water insoluble wax.
  • the limiting size of Q depends on R, Z, and M + .
  • sodium sulfoethyl methacrylate is a highly acceptable copolymerizable ionic material for use in the present invention.
  • R and Z are governed by the reactivity needed, and the selection of Q is usually determined by the reaction used to attach the sulfonic acid to the base monomer (or vice versa).
  • Latexes are known, such latexes being commercially available and being referred to herein as "self-stabilizing latexes", that is, latexes, the polymeric particles of which contain in the polymer molecule functional groups that are effective in maintaining the polymeric particles dispersed in the aqueous phase of the latex.
  • self-stabilizing latexes that is, latexes, the polymeric particles of which contain in the polymer molecule functional groups that are effective in maintaining the polymeric particles dispersed in the aqueous phase of the latex.
  • such latexes do not require the presence of an external surfactant to maintain the particles in their dispersed state.
  • Latexes of this type generally have a surface tension very close to that of water (about 72 dynes/cm). It has been observed that autodepositing compositions containing such latexes form coatings which build up at a relatively fast rate.
  • An exemplary method for preparing such latexes involves preparation of an aqueous dispersion by an essentially continuous, carefully controlled addition of the requisite polymerization constituents (including polymerization initiator systems, if desired) to the aqueous medium having the desired pH value, followed by the subsequent addition of the necessary polymerization initiator, to form a polymeric seed latex in order to aid in the control of particle size.
  • the requisite polymerization constituents including polymerization initiator systems, if desired
  • the necessary polymerization initiator to form a polymeric seed latex in order to aid in the control of particle size.
  • very small amounts of conventional surfactants such as alkali soaps or the like, may be incorporated in the aqueous medium to further aid in the attainment of particles of desired size.
  • Highly stable polymer latexes for use in the present invention are characterized by the virtual absence of undesirable coagulum which often results when polymeric latexes are stabilized by conventional water soluble surfactants.
  • Such latexes combine the highly beneficial properties of optimum colloidal stability, reduced viscosities at relatively high polymer solids content, low foaming tendencies, and excellent product uniformity and reproducibility.
  • Such highly stable latexes which are internally stabilized are disclosed, for example, in U.S. Pat. No. 3,617,368.
  • a preferred embodiment of this invention comprises the use of vinylidene chloride-containing latexes in which a water soluble ionic material such as, for example, sodium sulfoethyl methacrylate is copolymerized with the comonomers comprising the copolymer.
  • a water soluble ionic material such as, for example, sodium sulfoethyl methacrylate is copolymerized with the comonomers comprising the copolymer.
  • Sodium sulfoethyl methacrylate is particularly effective for use with monomeric vinylidene chloride and the relatively hydrophilic monomers methyl methacrylate or methacrylic acid when used in the amounts and in the manner described herein.
  • Latexes for use in this invention are latexes with about 35 to about 60 weight % solids comprising a polymeric composition prepared by emulsion polymerization of vinylidene chloride with one or more comonomers selected from the group consisting of vinyl chloride, acrylic acid, a lower alkyl acrylate (such as methyl acrylate, ethyl acrylate, butyl acrylate), methacrylic acid, methyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide and stabilized with sulfonic acid or sulfonic acid salt of the formula R--Z--(CH 2 ) n --(SO 3 ) - M + , wherein R represents vinyl or lower alkyl-substituted vinyl; Z represents one of the difunctional groups: ##STR2## where T represents hydrogen or an alkyl group; n is an integer from 1 to 20 (preferably 1 to 6), and M + is hydrogen or an alkyl
  • a subgroup of preferred polymers are those having at least about 50% by weight of vinylidene chloride, but less than about 70%, and about 5 to about 35% vinyl chloride, and about 5 to about 20% of a vinyl compound selected from the group consisting of acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide and methacrylamide, and combinations thereof, and about 1 to about 3% by weight of sulfoethyl methacrylate.
  • a particularly preferred group of latexes are latexes containing about 30 to about 70 weight % of solids formed by emulsion polymerization of about 50 to about 99% vinylidene chloride based on total weight of polymer and about 0.1 to about 5% by weight of sulfoethyl methacrylate, with optionally other comonomers selected from the group consisting of vinyl chloride, acrylic and methacrylic monomers such as acrylonitriles, acrylamides, methacrylamides and mixtures thereof in amounts between about 5 and about 50% by weight, and substantially free of unpolymerized surfactant or protective colloid.
  • resin for use prior to treatment according to this invention are dispersions of copolymers of about 50 to about 90% by weight of butyl acrylate and about 1 to about 2% by weight of sulfoethyl methacrylate based on the total weight of polymer.
  • Another preferred subclass of polymers are the latexes of vinylidene chloride-containing polymers internally stabilized with sulfoethyl methacrylate and free of surfactant, and including optionally vinyl chloride and one or more acrylic comonomers.
  • Another preferred vinylidene chloride-containing copolymer is one comprising about 15 to about 20 weight % vinyl chloride, about 2 to about 5 weight % butyl acrylate, about 3 to about 10 weight % acrylonitrile, about 1 to about 2 weight % sulfoethyl methacrylate.
  • This particular copolymer will have less than 70% by weight vinylidene chloride copolymer based upon total weight of comonomers (including the sulfoethyl methacrylate) used in the emulsion polymerization.
  • the amount of the resin comprising the coating composition can vary over a wide range.
  • the lower concentration limit of the resin particles in the composition is dictated by the amount of resin needed to provide sufficient material to form a resinous coating.
  • the upper limit is dictated by the amount of resin particles which can be dispersed in the acidic aqueous composition. In general, the higher the amount of resin particles in the composition, the heavier the coating formed, other factors being the same.
  • coating compositions can be formulated with a range of about 5 to about 550 g/l of resin solids, the amount of the resin solids will tend to vary depending on the other ingredients comprising the composition and also on the specific latex or resin used. For many applications, good results can be achieved by utilizing about 50 to about 100 g/l of resin solids in the composition.
  • Optional ingredients can be added to the composition as desired.
  • suitable pigments can be included in the composition.
  • pigments that can be used are carbon black, phthalocyanine blue, phthalocyanine green, quinacridone red, benzidene yellow, and titanium dioxide.
  • the pigment should be added to the composition in an amount which imparts to the coating the desired color and/or the desired depth or degree of hue. It should be understood that the specific amount used will be governed by the specific pigment used and the color of coating desired. Excellent results have been achieved by using the aqueous dispersion in an amount such that the composition contains about 0.2 to about 3 g of furnace black/100 g of resin solids.
  • pigments are available in aqueous dispersions which may include surfactants or dispersing agents for maintaining the pigment particles in dispersed state. When utilizing such pigment dispersions, they should be selected so that the surfactant concentration in the aqueous phase of the composition is below the critical micelle concentration ("CMC"), preferably below the surfactant concentration which corresponds to the inflection point on a graph of surface tension versus the logarithm of surfactant concentration in the composition. Suitable pigmented compositions are illustrated in examples herein.
  • CMC critical micelle concentration
  • Colored coatings can be produced also by the use of dyes, examples of which include rhodamine derived dyes, methyl violet, safranine, anthraquinone derived dyes, nigrosine, and alizarin cyanine green. These are but a few examples of dyes that can be used.
  • additives examples include those generally known to be used in formulating paint compositions, for example, UV stabilizers, viscosity modifiers, etc.
  • the total amount of surfactant in the aqueous phase of the composition should be maintained below the CMC.
  • the aqueous phase of the composition contains little or no surfactant.
  • the preferred surfactants are the anionic surfactants.
  • suitable anionic surfactants are the alkyl, alkyl/aryl or naphthalene sulfonates, for example, sodium dioctylsulfosuccinate and sodium dodecylbenzene sulfonate.
  • the constituents thereof can be admixed in any suitable way, for example, as described in U. S. Pat. No. 4,191,676.
  • the bath be prepared by admixing:
  • an aqueous concentrate comprising about 350 to about 550 g/l of resin particles, preferable the aforementioned vinylidene chloride-containing resin particles, and about 10 to about 550 g/l of pigment;
  • aqueous concentrate prepared from about 0.4 to about 210 g/l of HF and a water soluble ferric-containing compound in an amount equivalent to about 1 to about 100 g/l of ferric iron.
  • the bath can be prepared by stirring water into concentrate (A) and thereafter admixing therewith the required amount of concentrate (B) with stirring to provide a homogenous composition.
  • Agitating the composition aids in maintaining it uniform and in improving the uniformity of the coatings formed. With other factors held constant, heating of the composition will result in heavier coatings. However, satisfactory results can be obtained by operating the coating process at ambient temperature, and this is generally preferred for convenience.
  • the freshly applied coating is rinsed with water after the coated surface has been withdrawn from the composition and before significant drying of the wet coating takes place.
  • Such water rinsing is effective in removing therefrom residuals, such as acid and other ingredients of the composition that adhere to the coated surface. If such residuals are allowed to remain on the coated surface, they may adversely affect the quality of the coating. Improvements in rendering the cured form of the coating more impermeable to water, as provided by the present invention, are not realized by simply water rinsing the freshly formed coating.
  • Exemplary means for applying an adhesion and corrosion resistance promoting solution according to this invention to the freshly formed coating include spray, mist, and immersion, with the preferred means of applying such solution being immersion of the uncured coated surface in the solution for a period of time of about 5 seconds to about 5 minutes.
  • the most preferred substrate for treatment according to this invention is a conventional automobile leaf spring made of high carbon steel and shot blasted on only one side.
  • shot blasting is believed to have at least a slight effect on the electrochemical activity of the steel, and the difference in such activity between the shot blasted and non shot blasted sides may have caused some of the difficulties noted in earlier attempts to use autodeposition for springs of this type.
  • the preferred activating system comprises a ferric ion-containing compound and hydrofluoric acid.
  • a preferred autodepositing composition comprises a soluble ferric ion containing compound in an amount equivalent to about 0.025 to about 3.5 g/l ferric iron, most preferably about 0.3 to about 1.6 g/l of ferric iron, and hydrofluoric acid in an amount sufficient to impart to the composition a pH within the range of about 1.6 to about 5.0.
  • the ferric-containing compounds are ferric nitrate, ferric chloride, ferric phosphate, ferric oxide, and ferric fluoride, the last mentioned being preferred.
  • alkaline components of the treatment solutions according to the invention are volatile or "fugitive".
  • Aqueous ammonium hydroxide and ammonium bicarbonate exemplify such fugitive bases, but the latter is less preferred, because when using it there is greater danger of blisters in the autodeposited coating after oven curing.
  • the coating should be cured. Fusion of the resinous coating renders it continuous, thereby improving its resistance to corrosion and its adherence to the underlying metallic surface.
  • the conditions under which the curing and/or fusion operation is carried out depend somewhat on the specific resin employed. In general, it is desirable to apply heat to fuse the resin, although some of the vinylidene chloride-containing resins described above can be cured at room temperature. Generally, the corrosion resistance, hardness and solvent resistance properties of coatings fused at elevated temperatures have been observed to be better than coatings which have been air dried. However, there are applications where air dried coatings can be used satisfactorily.
  • the fusion of the coating should be carried out under temperature and time conditions which do not adversely affect the desired properties of the coating. Exemplary conditions used in fusing the vinylidene chloride-containing coatings are temperatures within the range of about 20° C. to 120° C. for periods of time within the range of about 10 to 30 minutes, depending on the mass of the coated part. Baking the coating for a period of time until the metallic surface has reached the temperature of the heated environment has been used effectively.
  • the coating When baked in an oven, the coating reaches the proper "curing" or heating temperature for the full development of coating properties when the metal part reaches that temperature. For this reason, parts that are constructed of thicker steel require longer times to reach the required temperature. For massive parts, it may not be possible to reach the required temperature without deleteriously affecting the coating and causing it to degrade.
  • infrared radiation curing it is possible to overcome this problem by resorting to infrared radiation curing. In this case, it is possible to cure the coating without simultaneously raising the temperature of the metal to the required temperature.
  • infrared radiation curing is practicable only for simple geometric shapes, since the area to be cured must be exposed to the infrared. In using infrared radiation curing, all coated surfaces must be accessible to the infrared source, that is, the entire coated surface must "see" the infrared.
  • the substrates coated for these examples were panels of high carbon spring steel as used for conventional automobile leaf springs. One side only of each panel had been shot blasted in a manner typical for the treatment of conventional automobile leaf springs before coating treatment was begun.
  • the process sequence used was:
  • ACRPS adhesion and corrosion resistance promoting treatment

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
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  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
US07/718,676 1991-01-24 1991-06-21 Treating an autodeposited coating with an alkaline solution containing anions of multifunctional organic acids Expired - Lifetime US5248525A (en)

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US07/718,676 US5248525A (en) 1991-01-24 1991-06-21 Treating an autodeposited coating with an alkaline solution containing anions of multifunctional organic acids
BR9205529A BR9205529A (pt) 1991-01-24 1992-01-21 Processo para a formacao de um revestimento organico autodepositado sobre as partes metalicas da superficie de um objeto
DE69204053T DE69204053T2 (de) 1991-01-24 1992-01-21 Behandlung einer autophoretischen beschichtung mit hilfe eines multifunktionelle organische säuren enthaltenden alkalischen mittels.
AU12658/92A AU655632B2 (en) 1991-01-24 1992-01-21 Treating an autodeposited coating with an alkaline solution containing anions of multifunctional organic acids
CA002098830A CA2098830C (fr) 1991-01-24 1992-01-21 Traitement d'un revetement auto-depose par electrolyse au moyen d'une solution alcaline qui contient des anions d'acides organiques multifonctionnels
ES92904730T ES2079855T3 (es) 1991-01-24 1992-01-21 Tratamiento de un revestimiento autodepositado con una solucion alcalina que contiene aniones de acidos organicos multifuncionales.
PCT/US1992/000490 WO1992012806A1 (fr) 1991-01-24 1992-01-21 Traitement d'un revetement autodepose a l'aide d'une solution alcaline renfermant des anions d'acides organiques multifonctionnels
EP92904730A EP0568619B1 (fr) 1991-01-24 1992-01-21 Traitement d'un revetement autodepose a l'aide d'une solution alcaline renfermant des anions d'acides organiques multifonctionnels
JP4009858A JP3012388B2 (ja) 1991-01-24 1992-01-23 多官能有機酸含有アルカリ水溶液による自己析出有機被膜の処理方法
MX9200318A MX9200318A (es) 1991-01-24 1992-01-24 Tratamientos de un revestimiento autodepositado con una solucion alcalina que contiene aniones de acidos organicos multifuncionales.

Applications Claiming Priority (2)

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US07/645,435 US5164234A (en) 1991-01-24 1991-01-24 Treating an autodeposited coating with an alkaline solution containing organophosphonate ions
US07/718,676 US5248525A (en) 1991-01-24 1991-06-21 Treating an autodeposited coating with an alkaline solution containing anions of multifunctional organic acids

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BR (1) BR9205529A (fr)
CA (1) CA2098830C (fr)
DE (1) DE69204053T2 (fr)
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WO1995004608A1 (fr) * 1993-08-11 1995-02-16 Henkel Corporation Composition et procede destines a un traitment prealable a la peinture de matieres plastiques
US5409737A (en) * 1992-03-06 1995-04-25 Henkel Corporation Process for separating multivalent metal ions from autodeposition compositions and process for regenerating chelating type ion exchange resins useful therewith
US5415895A (en) * 1993-06-25 1995-05-16 Texo Corporation Method for producing improved coating composition with corrosion resistance
WO1997004880A1 (fr) * 1995-07-25 1997-02-13 Henkel Corporation Composition et procede de depot automatique a l'aide d'une solution de rincage modificatrice du film de revetement mouille, depose automatiquement
WO1997009127A1 (fr) * 1995-09-06 1997-03-13 Henkel Corporation Traitement de preparation par sous-couche pour depot automatique
US5632438A (en) * 1995-10-12 1997-05-27 International Business Machines Corporation Direct chip attachment process and apparatus for aluminum wirebonding on copper circuitization
US5711996A (en) * 1995-09-28 1998-01-27 Man-Gill Chemical Company Aqueous coating compositions and coated metal surfaces
US5750198A (en) * 1993-08-11 1998-05-12 Henkel Corporation Composition and process for prepainting treatment of plastics
US5786030A (en) * 1996-11-12 1998-07-28 Henkel Corporation Spotting resistant gloss enhancement of autodeposition coating
WO2000017269A1 (fr) * 1998-09-23 2000-03-30 Henkel Corporation Compositions aqueuses autodeposantes comprenant des polymeres disperses non-filmogenes
US6143365A (en) * 1998-06-03 2000-11-07 Henkel Corporation Autodeposited coating with improved thermal stability and composition and process therefor
US6410092B1 (en) 1999-05-21 2002-06-25 Henkel Corporation Autodeposition post-bath rinse process
US20040094236A1 (en) * 2002-11-14 2004-05-20 Crown Technology, Inc. Methods for passivating stainless steel
US20060214137A1 (en) * 2005-03-25 2006-09-28 Bulk Chemicals, Inc. Phosphonic acid and polyvinyl alcohol conversion coating
EP4310223A1 (fr) 2022-07-18 2024-01-24 Henkel AG & Co. KGaA Rinçage par réaction alcaline pour revêtements autophorétiques décoratifs
US12180384B2 (en) 2019-07-12 2024-12-31 Henkel Ag & Co. Kgaa Single layer autodepositable coating formulation

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US5300323A (en) * 1992-10-21 1994-04-05 Henkel Corporation Reducing or avoiding pinhole formation in autodeposition on zinciferous surfaces
US6033492A (en) * 1995-07-25 2000-03-07 Henkel Corporation Composition and process for autodeposition with modifying rinse of wet autodeposited coating film
GB9725898D0 (en) * 1997-12-08 1998-02-04 Albright & Wilson Process for treating metal surfaces
US6395336B1 (en) 1998-01-14 2002-05-28 Henkel Corporation Process for improving the corrosion resistance of a metal surface

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US4828615A (en) * 1986-01-27 1989-05-09 Chemfil Corporation Process and composition for sealing a conversion coated surface with a solution containing vanadium
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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5409737A (en) * 1992-03-06 1995-04-25 Henkel Corporation Process for separating multivalent metal ions from autodeposition compositions and process for regenerating chelating type ion exchange resins useful therewith
US5415895A (en) * 1993-06-25 1995-05-16 Texo Corporation Method for producing improved coating composition with corrosion resistance
WO1995004608A1 (fr) * 1993-08-11 1995-02-16 Henkel Corporation Composition et procede destines a un traitment prealable a la peinture de matieres plastiques
US5750198A (en) * 1993-08-11 1998-05-12 Henkel Corporation Composition and process for prepainting treatment of plastics
WO1997004880A1 (fr) * 1995-07-25 1997-02-13 Henkel Corporation Composition et procede de depot automatique a l'aide d'une solution de rincage modificatrice du film de revetement mouille, depose automatiquement
WO1997009127A1 (fr) * 1995-09-06 1997-03-13 Henkel Corporation Traitement de preparation par sous-couche pour depot automatique
AU711181B2 (en) * 1995-09-06 1999-10-07 Henkel Corporation Precoat conditioning treatment for autodeposition
US5868820A (en) * 1995-09-28 1999-02-09 Ppg Industries, Inc. Aqueous coating compositions and coated metal surfaces
US5711996A (en) * 1995-09-28 1998-01-27 Man-Gill Chemical Company Aqueous coating compositions and coated metal surfaces
US5632438A (en) * 1995-10-12 1997-05-27 International Business Machines Corporation Direct chip attachment process and apparatus for aluminum wirebonding on copper circuitization
US5786030A (en) * 1996-11-12 1998-07-28 Henkel Corporation Spotting resistant gloss enhancement of autodeposition coating
US6143365A (en) * 1998-06-03 2000-11-07 Henkel Corporation Autodeposited coating with improved thermal stability and composition and process therefor
WO2000017269A1 (fr) * 1998-09-23 2000-03-30 Henkel Corporation Compositions aqueuses autodeposantes comprenant des polymeres disperses non-filmogenes
US6559204B1 (en) 1998-09-23 2003-05-06 Henkel Corporation Autodepositable aqueous compositions including dispersed non-film-forming polymers
US6410092B1 (en) 1999-05-21 2002-06-25 Henkel Corporation Autodeposition post-bath rinse process
US20040094236A1 (en) * 2002-11-14 2004-05-20 Crown Technology, Inc. Methods for passivating stainless steel
US20060214137A1 (en) * 2005-03-25 2006-09-28 Bulk Chemicals, Inc. Phosphonic acid and polyvinyl alcohol conversion coating
US7935274B2 (en) 2005-03-25 2011-05-03 Bulk Chemicals, Inc. Phosphonic acid and polyvinyl alcohol conversion coating
US12180384B2 (en) 2019-07-12 2024-12-31 Henkel Ag & Co. Kgaa Single layer autodepositable coating formulation
EP4310223A1 (fr) 2022-07-18 2024-01-24 Henkel AG & Co. KGaA Rinçage par réaction alcaline pour revêtements autophorétiques décoratifs
WO2024017544A1 (fr) 2022-07-18 2024-01-25 Henkel Ag & Co. Kgaa Rinçage par réaction alcaline pour revêtements autophorétiques décoratifs

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EP0568619B1 (fr) 1995-08-09
BR9205529A (pt) 1994-04-19
MX9200318A (es) 1992-07-01
EP0568619A1 (fr) 1993-11-10
JP3012388B2 (ja) 2000-02-21
CA2098830C (fr) 2003-03-25
ES2079855T3 (es) 1996-01-16
DE69204053T2 (de) 1996-04-04
CA2098830A1 (fr) 1992-07-25
WO1992012806A1 (fr) 1992-08-06
DE69204053D1 (de) 1995-09-14
AU655632B2 (en) 1995-01-05
JPH05186889A (ja) 1993-07-27
AU1265892A (en) 1992-08-27

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